1. Field of the Invention
This invention relates to processes for producing 1,3-difunctional compounds by the acid catalyzed reaction of an olefin with an aldehyde or aldehyde precursor.
2. Description of the Prior Art
Numerous modifications of the acid catalyzed reaction of olefin with aldehyde or aldehyde precursor (i.e., the Prins Reaction) to provide a variety of open chain and cyclic organic compounds are known.
In one category of reaction, olefin and aldehyde are co-reacted to largely produce formals, or cyclic diethers. U.S. Pat. No. 2,135,454 to McAlevy describes such a reaction, employing a catalyst system based upon a halogen acid and a boric acid, to provide formals. U.S. Pat. Nos. 2,158,031 and 2,289,548 to Lodger describe the reaction of formaldehyde and propylene to provide a substituted dioxane.
In accordance with U.S. Pat. No. 2,362,307 to Ritter, meta-dioxane is produced by reacting an aldehyde with an olefin in the presence of sulfuric acid. In the process of making meta-dioxanes disclosed in U.S. Pat. No. 2,368,494 to Rosen, tertiary unsaturated compounds are reacted with aldehydes in the presence of a dilute aqueous solution of boron trifluoride and optionally, a mineral acid such as sulfuric, hydrofluoric, hydrochloric or phosphoric acid. U.S. Pat. No. 2,423,783 to Lippincott relates to the preparation of 1,3-diols by the reaction of methyl alcohol with a 1,3-dioxane which has been obtained by the condensation of olefins and aldehydes. U.S. Pat. No. 2,426,017 to Hamblet, et al. and U.K. Specification No. 590,571 report that improved yields of 1,3-alkanediol cyclic formals can be obtained by including a small quantity of the formal along with the reactants propylene and formaldehyde. In addition, U.K. Specification No. 590,571 discloses formic acid as a catalyst for the reaction. U.S. Pat. No. 2,490,276 to Munday describes the reaction of 2,3-dimethyl butene-2 with formaldehyde in the presence of metallic chlorides such as stannic chloride, mercuric chloride and titanium chloride, or sulfuric or hydrochloric acid, to produce a cyclic diether. As disclosed in U.S. Pat. No. 2,504,732 to Rosen, aldehydes are condensed with olefins in the presence of aqueous boron fluorides to produce meta-dioxanes. In the process described in U.S. Pat. No. 2,997,480 to Hellin, isobutene is reacted with formaldehyde in the presence of a strong inorganic acid to provide 4,5-dimethylmetadioxane. According to U.S. Pat. No. 3,062,835 to Signorino, 2-methylbutene-2 is selectively reacted with formaldehyde in the presence of 2-methylbutene-1 and sulfuric acid to provide 4,4,5-trimethyl-meta-dioxane. U.S. Pat. No. 3,154,563 and French Pat. No. 1,292,840 each describe the use of an acidic cation-exchange resin catalyst in the reaction of isobutene and formaldehyde to provide 4,4-dimethyldioxane. Following the process described in U.S. Pat. No. 3,414,588 to Jones, aldehydes and olefins are co-reacted in the presence of a base exchanged alumino-silicate catalyst to provide alkyl-meta-dioxane. U.S. Pat. No. 3,438,977 to Fetterly, et al. describes the production of meta-dioxanes or acetate esters by the reaction of olefin and aldehyde in a diluent such as acetic acid, propionic acid or butyric acid, in the presence of cationic exchange resins which contain sulfonic, phosphonic, phosphonous, arsenic and like acid groups. From U.S. Pat. No. 3,818,043 to Starks, it is known to prepare a mixture containing unsaturated 1-alcohols, diols and dioxanes by the reaction of olefin and aldehyde in the presence of an aqueous solution of a strong acid such as sulfuric acid and cuprous chloride. U.S. Pat. No. 4,017,518 to Gorbunov, et al. describes the preparation of 4,4-dimethyldioxane-1,3 by reacting isobutylene with formaldehyde in the presence of an inorganic salt of a mineral acid. U.S. Pat. No. 4,069,232 to Horvitz, et al. discloses the preparation of, among others, meta-dioxanes, by the protic acid catalyzed reaction of an olefin with an aldehyde. 1,3-Dioxane can be produced, along with various esters and other compounds, when acetic acid is present in the reaction media.
In another category of reaction, olefin and aldehyde are co-reacted primarily to provide glycol monoesters and diesters. Illustrative of such a reaction are U.S. Pat. Nos. 3,438,997 to Fetterly, et al. and 4,069,232 to Horvitz, et al., and French Pat. Nos. 717,712 and 933,182, each of which describes the reaction of aldehyde and olefin in the presence of a carboxylic acid and a strong mineral acid to provide glycol esters. U.S. Pat. No. 3,438,997 to Fetterly, et al. specifically relates to the preparation of metadioxanes or acetate esters by the reaction of olefin and aldehyde in a lower alkyl monocarboxylic acid, e.g., acetic acid, propionic acid or butyric acid, in the presence of acidic cationic exchange resins. U.S. Pat. No. 4,069,232 to Horvitz, et al. discloses the preparation, inter alia, of glycol monoesters and diesters by the reaction of olefin with an aldehyde in the presence of a carboxylic acid employing a protic acid such as hydriodic acid or hydrobromic acid. French Pat. Nos. 717,712 and 933,182 each disclose the preparation of glycol esters by the reaction of an olefin with an aldehyde in the presence of acetic acid and sulfuric acid as catalyst.
Another category of the Prins Reaction yields glycols for the most part. According to U.S. Pat. No. 2,143,370 to Fitzky, butylene glycol is obtained by reacting propylene with formaldehyde in the presence of a hydrogen halide and optionally, a heavy metal halide such as zinc chloride, calcium chloride, magnesium chloride or mercury chloride. In U.S. Pat. No. 2,368,494 to Rosen, 1,3-butylene glycols are obtained by reacting tertiary unsaturated compounds with aldehydes in the presence of a dilute aqueous solution of boron trifluoride and optionally, a mineral acid.
Glycols are prepared in accordance with the process of U.S. Pat. No. 2,449,001 to Mikeska, et al. by reacting an olefin with an aldehyde in the presence of a dilute ternary or quaternary mineral acid such as sulfuric, sulfurous, phosphoric, phosphorous, fluosulfonic, fluosilicic, dihydroxy fluoboric, and hydrofluoboric acids or acid-acting metallic salts of polybasic mineral acids such as NaHSO.sub.4, NaH.sub.2 PO.sub.4, ZnSO.sub.4, Fe.sub.2 (SO.sub.4).sub.3 or Al.sub.2 (SO.sub.4).sub.3. The process for preparing glycols disclosed in U.S. Pat. No. 3,414,588 to Jones calls for reacting aldehydes and olefins in the presence of a base exchanged aluminosilicate catalyst. The process of U.S. Pat. No. 3,818,043 to Starks referred to above provides a mixture of 1-alcohols, diols and dioxanes. U.S. Pat. No. 4,069,232 to Horvitz, et al. describes the protic acid catalyzed reaction of olefin and aldehyde to provide 1,3-glycols and a variety of other 1,3-difunctional compounds. Related processes for obtaining 1,3-difunctional compounds are described elsewhere. For example, see Arundale & Mikeska, Chem. Revs. 51, 505-55 (1952); Roberts, Friedel Craft and Related Reactions, Olah ed., Volume II, pages 1175-1210, Inter Science Publishers, New York, 1964; Walker, Formaldehyde, 3rd Ed. Reinhold Publishing Corp., New York, 1964, pages 416-28; and U.S. Pat. No. 3,586,698 to Ishii, et al.
Finally, the reaction of olefin and aldehyde can be made to provide halogenated alcohols and esters as described in U.S. Pat. No. 4,069,232 to Horvitz, et al. in which a mixture of 3-hydroxypropyliodide and its corresponding acetic acid ester 3-iodopropylacetate is obtained by reacting ethylene with formaldehyde in the presence of acetic acid and hydriodic acid.